Pesticide compositions exhibiting enhanced activity and methods for preparing same

ABSTRACT

Pest controlling compositions exhibiting enhanced pesticidal activity levels and methods for preparing the same are disclosed. In one embodiment, a method includes providing a liquid composition that includes at least one pesticide and at least one co-ingredient that enhances pesticidal activity of the composition compared to a composition dissimilar only in not having the at least one co-ingredient. The at least one co-ingredient may include at least one metal oxide, a combination of at least one transition metal salt and at least one proteinaceous material or a combination of at least one proteinaceous material and at least one polymeric material. The method further includes spray drying the liquid composition to provide a solid composition. In one aspect of this embodiment, the solid composition provided by the spray drying exhibits enhanced pesticidal activity compared to the liquid composition.

CROSS REFERENCE TO RELATED APPLICATIONS

The subject application claims priority to U.S. Provisional ApplicationNo. 61/214,989 filed Apr. 30, 2009, the contents of which areincorporated herein by reference in their entirety, and to U.S.Provisional Application No. 61/277,974 filed Oct. 1, 2009, the contentsof which are also incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The invention disclosed in this document is related to the field ofpesticides and their use in controlling pests.

BACKGROUND OF THE INVENTION

Pests cause millions of human deaths around the world each year.Furthermore, there are more than ten thousand species of pests thatcause losses in agriculture. These agricultural losses amount tobillions of U.S. dollars each year. Termites cause damage to variousstructures such as homes. These termite damage losses amount to billionsof U.S. dollars each year. As a final note, many stored food pests eatand adulterate stored food. These stored food losses amount to billionsof U.S. dollars each year, but more importantly, deprive people ofneeded food.

Many pesticide compositions have been developed over time to destroypests and alleviate the damages they cause. These compositions are oftenapplied to the environment in which the insects or other pests live orwhere their eggs are present, including the air surrounding them, thefood they eat, or objects which they contact. Several of thesecompositions are vulnerable to chemical and physical degradation whenapplied to these environments. If these types of degradation occur, thepesticidal activity of the pesticides can be adversely affected,commonly necessitating an increase in the concentration at which thepesticides are applied and/or more frequent applications of thepesticides. As a result, user costs and the cost to consumers canescalate. Therefore, a need exists for new pesticide compositions thatexhibit increased stability and enhanced activity compared to existingpesticide compositions when, for example, the pesticide compositions areapplied to an environment to control pests.

SUMMARY OF THE INVENTION

The present invention concerns novel pesticide compositions, methods forpreparing the compositions, and their use in controlling insects andcertain other invertebrates. In one embodiment, a method includesproviding a liquid composition that includes at least one pesticide andat least one co-ingredient that enhances pesticidal activity of thecomposition compared to a composition dissimilar only in not having theat least one co-ingredient. The at least one co-ingredient includes atleast one metal oxide, a combination of at least one transition metalsalt and at least one proteinaceous material, or a combination of atleast one proteinaceous material and at least one polymeric material.The method further includes spray drying the liquid composition toprovide a solid composition which may be, for example, in a powder orgranular form. In one form of this method, the at least one pesticide isa macrocyclic lactone insecticide.

In another form of this method, the at least one pesticide is aspinosyn, such as spinetoram or spinosad. However, it should beappreciated that alternatives for the at least one pesticide arecontemplated. In one aspect of the method, the liquid compositionfurther includes water and the spray drying includes at least partiallydehydrating or dyring the liquid composition such that the liquidcomposition includes a greater percentage of water, by weight, than thesolid composition. In yet another aspect of the method, the at least onepesticide and the at least one co-ingredient are present in the liquidcomposition at a ratio, by weight, that is substantially equivalent to aratio, by weight, at which the at least one pesticide and the at leastone co-ingredient are present in the solid composition. Still, anotheraspect of the method includes applying to a locus where control isdesired an insect-inactivating amount of the solid composition.

In another embodiment, a method includes providing a liquid compositionthat includes at least one pesticide and at least one co-ingredient thatenhances pesticidal activity of the composition compared to acomposition dissimilar only in not having the at least oneco-ingredient. The method further includes spray drying the liquidcomposition to provide a solid composition that exhibits enhancedpesticidal activity compared to the liquid composition. In one aspect ofthis method, the liquid composition includes a ratio by weight betweenthe at least one pesticide and the at least one co-ingredient which issubstantially equivalent to a ratio by weight between the at least onepesticide and the at least one co-ingredient in the solid composition.In another aspect of this method, the liquid composition furtherincludes water and the spray drying includes at least partiallydehydrating or drying the liquid composition. In a further aspect, thedehydrating or drying includes reducing water from at least about 20% byweight in the liquid composition to less than about 10% by weight in thesolid composition. Still, it should be appreciated that furthervariations in the reduction of water from the liquid composition to thesolid composition are contemplated.

In one other embodiment, a method includes providing a liquidcomposition that includes spinetoram, ferric oxide and a polymericmaterial that includes polyvinyl pyrrolidone. The method furtherincludes spray drying the liquid composition to provide a solidcomposition.

In yet another embodiment, a composition includes a solid materialincluding at least one pesticide and at least one co-ingredient thatenhances pesticidal activity of the composition compared to acomposition dissimilar only in not having the at least oneco-ingredient. Additionally, the solid material exhibits enhancedpesticidal activity compared to a liquid composition that includes theat least one pesticide and the at least one co-ingredient in a ratio byweight that is substantially equivalent to a ratio by weight between theat least one pesticide and the at least one co-ingredient in the solidmaterial.

Still, further embodiments, forms, features, aspects, benefits, objects,and advantages of the present invention shall become apparent from thedetailed description and examples provided.

DETAILED DESCRIPTION OF THE INVENTION

Throughout this document, all temperatures are given in degrees Celsius,and all percentages are weight percentages unless otherwise stated.

Pesticide compositions exhibiting increased stability and enhancedpesticidal activity are described in this document. More particularly,in one or more embodiments, the pesticide compositions exhibit enhancedresidual pesticidal activity. A pesticide is herein defined as anycompound which shows some pesticidal or biocidal activity, or otherwiseparticipates in the control or limitation of pest populations. Suchcompounds include fungicides, insecticides, nematocides, miticides,termiticides, rodenticides, molluscides, arthropodicides, herbicides,biocides, as well as pheromones and attractants and the like.

Examples of pesticides that can be included in the compositionsdescribed herein include, but are not limited to, antibioticinsecticides, macrocyclic lactone insecticides (for example, avermectininsecticides, milbemycin insecticides, and spinosyn insecticides),arsenical insecticides, botanical insecticides, carbamate insecticides(for example, benzofuranyl methylcarbamate insecticides,dimethylcarbamate insecticides, oxime carbamate insecticides, and phenylmethylcarbamate insecticides), diamide insecticides, desiccantinsecticides, dinitrophenol insecticides, fluorine insecticides,formamidine insecticides, fumigant insecticides, inorganic insecticides,insect growth regulators (for example, chitin synthesis inhibitors,juvenile hormone mimics, juvenile hormones, moulting hormone agonists,moulting hormones, moulting inhibitors, precocenes, and otherunclassified insect growth regulators), nereistoxin analogueinsecticides, nicotinoid insecticides (for example, nitroguanidineinsecticides, nitromethylene insecticides, and pyridylmethylamineinsecticides), organochlorine insecticides, organophosphorusinsecticides, oxadiazine insecticides, oxadiazolone insecticides,phthalimide insecticides, pyrazole insecticides, pyrethroidinsecticides, pyrimidinamine insecticides, pyrrole insecticides,tetramic acid insecticides, tetronic acid insecticides, thiazoleinsecticides, thiazolidine insecticides, thiourea insecticides, ureainsecticides, as well as, other unclassified insecticides.

Some of the particular insecticides that can be employed in thecompositions described in this document include, but are not limited to,the following: 1,2-dichloropropane, 1,3 dichloropropene, abamectin,acephate, acetamiprid, acethion, acetoprole, acrinathrin, acrylonitrile,alanycarb, aldicarb, aldoxycarb, aldrin, allethrin, allosamidin,allyxycarb, alpha-cypermethrin, alpha-endosulfan, amidithion, aminocarb,amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos,azinphos-ethyl, azinphosmethyl, azothoate, barium hexafluorosilicate,barthrin, bendiocarb, benfuracarb, bensultap, beta-cyfluthrin,beta-cypermethrin, bifenthrin, bioallethrin, bioethanomethrin,biopermethrin, bioresmethrin, bistrifluron, borax, boric acid, boricacid, bromfenvinfos, bromocyclen, bromo-DDT, bromophos, bromophosethyl,bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate,butoxycarboxim, cadusafos, calcium arsenate, calcium polysulfide,camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbontetrachloride, carbophenothion, carbosulfan, cartap,chlorantraniliprole, chlorbicyclen, chlordane, chlordecone,chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos, chloroform, chloropicrin, chlorphoxim,chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos,chromafenozide, cinerin I, cinerin II, cismethrin, cloethocarb,closantel, clothianidin, copper acetoarsenite, copper arsenate, coppernaphthenate, copper oleate, coumaphos, coumithoate, crotamiton,crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate,cyclethrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin,cyphenothrin, cyromazine, cythioate, DDT, decarbofuran, deltamethrin,demephion, demephion-O, demephion-S, demeton, demeton-methyl, demeton-O,demeton-O-methyl, demeton-S, demeton-S-methyl, demeton-S-methylsulphon,diafenthiuron, dialifos, diatomaceous earth, diazinon, dicapthon,dichlofenthion, dichlorvos, dicresyl, dicrotophos, dicyclanil, dieldrin,diflubenzuron, dilor, dimefluthrin, dimefox, dimetan, dimethoate,dimethrin, dimethylvinphos, dimetilan, dinex, dinoprop, dinosam,dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion,disulfoton, dithicrofos, d-limonene, DNOC, doramectin, ecdysterone,emamectin, EMPC, empenthrin, endosulfan, endothion, endrin, EPN,epofenonane, eprinomectin, esfenvalerate, etaphos, ethiofencarb, ethion,ethiprole, ethoate-methyl, ethoprophos, ethyl formate, ethyl-DDD,ethylene dibromide, ethylene dichloride, ethylene oxide, etofenprox,etrimfos, EXD, famphur, fenamiphos, fenazaflor, fenchlorphos,fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxacrim,fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion,fenthion-ethyl, fenvalerate, fipronil, flonicamid, flubendiamide,flucofuron, flucycloxuron, flucythrinate, flufenerim, flufenoxuron,flufenprox, fluvalinate, fonofos, formetanate, formothion, formparanate,fosmethilan, fospirate, fosthietan, furathiocarb, furethrin,gamma-cyhalothrin, gamma-HCH, halfenprox, halofenozide, HCH, HEOD,heptachlor, heptenophos, heterophos, hexaflumuron, HHDN, hydramethylnon,hydrogen cyanide, hydroprene, hyquincarb, imidacloprid, imiprothrin,indoxacarb, iodomethane, IPSP, isazofos, isobenzan, isocarbophos,isodrin, isofenphos, isoprocarb, isoprothiolane, isothioate, isoxathion,ivermectin, jasmolin I, jasmolin II, jodfenphos, juvenile hormone I,juvenile hormone II, juvenile hormone III, kelevan, kinoprene,lambda-cyhalothrin, lead arsenate, lepimectin, leptophos, lindane,lirimfos, lufenuron, lythidathion, malathion, malonoben, mazidox,mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride,mesulfenfos, metaflumizone, methacrifos, methamidophos, methidathion,methiocarb, methocrotophos, methomyl, methoprene, methoxychlor,methoxyfenozide, methyl bromide, methylchloroform, methylene chloride,metofluthrin, metolcarb, metoxadiazone, mevinphos, mexacarbate,milbemectin, milbemycin oxime, mipafox, mirex, monocrotophos,morphothion, moxidectin, naftalofos, naled, naphthalene, nicotine,nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron,noviflumuron, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos,oxydisulfoton, para-dichlorobenzene, parathion, parathion-methyl,penfluron, pentachlorophenol, permethrin, phenkapton, phenothrin,phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor,phosphamidon, phosphine, phoxim, phoxim-methyl, pirimetaphos,pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, potassium arsenite,potassium thiocyanate, pp′-DDT, prallethrin, precocene I, precocene II,precocene III, primidophos, profenofos, profluthrin, promacyl,promecarb, propaphos, propetamphos, propixur, prothidathion, prothiofos,prothoate, protrifenbute, pyraclofos, pyrafluprole, pyrazophos,pyresmethrin, pyrethrin I, pyrethrin II, pyridaben, pyridalyl,pyridaphenthion, pyrifluquinazon, pyrimidifen, pyrimitate, pyriprole,pyriproxyfen, quassia, quinalphos, quinalphosmethyl, quinothion,rafoxanide, resmethrin, rotenone, ryania, sabadilla, schradan,selamectin, silafluofen, silica gel, sodium arsenite, sodium fluoride,sodium hexafluorosilicate, sodium thiocyanate, sophamide, spinetoram,spinosad, spiromesifen, spirotetramat, sulcofuron, sulfluramid,sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE,tebufenozide, tebufenpyrad, tebupirimfos, teflubenzuron, tefluthrin,temephos, TEPP, terallethrin, terbufos, tetrachloroethane,tetrachlorvinphos, tetramethrin, theta-cypermethrin, thiacloprid,thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb,thiofanox, thiometon, thiosultap, thuringiensin, tolfenpyrad,tralomethrin, transfluthrin, transpermethrin, triarathene, triazamate,triazophos, trichlorfon, trichlormetaphos-3, trichloronat, trifenofos,triflumuron, trimethacarb, triprene, vamidothion, vaniliprole, XMC,xylylcarb, zeta-cypermethrin, zolaprofos, and α-ecdysone.

Additionally, it is contemplated that any combination of the aboveinsecticides can be employed in the compositions described herein. Formore information consult “COMPENDIUM OF PESTICIDE COMMON NAMES” locatedat http://www.alanwood.net/pesticides/index.html. Also consult “THEPESTICIDE MANUAL” 14th Edition, edited by C D S Tomlin, copyright 2006by British Crop Production Council.

Various pesticides are susceptible to chemical and physical degradationin the presence of certain environmental influences, such as heat and/orlight. Pesticides that are susceptible to degradation with respect tothe latter of these influences are commonly referred to as“photo-labile.” With respect to at least some photo-labile pesticides,it is believed that their degradation can be attributed to a reactionwith singlet oxygen. Examples of pesticides that are reactive withsinglet oxygen include, but are not limited to, certain olefins,aromatics, phenols, naphthols, furans, pyrans and other heterocyclescontaining oxygen; pyrroles, oxazoles, imidazoles, indoles and otherheterocycles containing nitrogen; aliphatic, alicyclic and aromaticamines; amino acids, peptides and proteins; and sulfur containingcompounds such as mercaptans and sulfides; and the like. Further detailsregarding the determination of whether a pesticide is reactive withsinglet oxygen are provided in International Patent Publication No. WO2007/053760. It should be appreciated that any one or combination of theaforementioned photo-labile, singlet oxygen reactive pesticides could beincluded in the compositions described herein.

More particular examples of photo-labile, singlet oxygen reactivepesticides that could be included either alone or in combination witheach other in the compositions described herein include, but are notlimited to, natural products which are microorganisms, microbialproducts, and materials derived or extracted from plants, animals, ormineral-bearing rocks. These natural products include products derivedfrom naturally derived soil dwelling organisms such as actinomycetebacteria such as, for example, macrocyclic lactone insecticides. Oneexemplary macrocyclic lactone insecticide includes avermectins andderivatives thereof, such as abamectin, doramectin, emamectin,eprinomectin, ivermectin and selamectin. Another exemplary macrocycliclactone insecticide includes milbemycins and derivatives thereof, suchas lepimectin, milbemectin, milbemycin oxime and moxidectin. Yet anotherexemplary macrocyclic lactone insecticide includes spinosyns, such asspinosad, and derivatives thereof such as synthetically producedspinetoram as disclosed in U.S. Pat. Nos. 5,227,295; 5,670,364;5,591,606; 6,001,981; 6,143,526; 6,455,504; 6,585,990; 6,919,464;5,362,634; 5,539,089; and 5,202,242, each of which is herebyincorporated herein by reference in its entirety. Other natural productsinclude sabadilla or veratrine, pyrethrum or pyrethrin, neem oil orazadirachtin, rotenone, ryania or ryanodine, Bacillus thuringiensis (B.t.), Bacillus subtilis, pheromones, natural attractants and the like.Other pesticides that could be included in the compositions describedherein can include synthetically produced pesticides which are reactivetoward singlet oxygen. Examples include, but are not limited toindoxacarb, imazalil and fenpropimorph. In addition to the foregoing, itshould be appreciated that the compositions described herein could alsoinclude at least one pesticide which is photo-labile or reactive withsinglet oxygen and at least one other pesticide which is not reactivewith singlet oxygen or otherwise photo-labile.

Compositions that include at least one or a mixture of theaforementioned pesticides and at least one co-ingredient that enhancesthe pesticidal activity of the composition compared to a compositiondissimilar only in not having the at least one co-ingredient haverecently been discovered. For example, it is contemplated that theactivity or half-life of the composition is extended and therefore thesame activity can be achieved with a lower amount of the compositionwhen compared to a composition dissimilar only in not having the atleast one co-ingredient. Additionally, or alternatively, it iscontemplated that improved pesticidal control over time is achieved withthe composition including the at least one co-ingredient when comparedto a composition dissimilar only in not having the at least oneco-ingredient.

In one embodiment, the at least one co-ingredient includes at least onemetal oxide and the composition exhibits enhanced pesticidal activitycompared to a composition dissimilar only in not having the metal oxide.As used herein, the term “metal oxide” is used to describe a compoundcontaining at least one oxygen atom and at least one metal atom. In oneform, the metal oxide is insoluble in water. Additionally oralternatively, it is contemplated that the metal oxide may be atransition metal oxide. Non-limiting examples of transition metal oxidesinclude zinc oxide; an iron oxide, such as ferrous (iron (II) oxide) orferric (iron (III) oxide) oxide as well as iron (II, III) oxide; acopper oxide, such as cuprous (copper (I) oxide) or cupric (copper (II)oxide) oxide; a titanium oxide, such as titanium dioxide (titanium (IV)oxide), titanium (II) oxide and titanium (III) oxide; a cobalt oxide,such as cobalt (II) oxide and cobalt (III) oxide; a nickel oxide, suchas nickel (II) oxide or nickel (III) oxide; a manganese oxide, such asmanganese (II, III) oxide; a chromium oxide, such as chromium (III)oxide or chromium (IV) oxide; silver oxide; palladium oxide; andlanthanum oxide. In one or more forms, the metal oxide may also be ahydroxide or part of a hydrate complex. Examples of these include zinchydroxide, partially dehydrated zinc hydroxide or zinc oxide hydroxide,iron (II) hydroxide, iron (III) hydroxide, iron oxide hydroxide,anhydrous or hydrated iron oxide and iron oxide hydroxide, manganesehydroxide, manganese oxide hydroxide, hydrated manganese hydroxide ormanganese oxide hydroxide, copper hydroxide, partially dehydrated copperhydroxide or copper oxide hydroxide, titanium hydroxide, titanium oxidehydroxide, hydrated titanium hydroxide or titanium oxide hydroxide, justto provide a few possibilities. It should be appreciated that acombination of one or more of the aforementioned metal oxides can beemployed in the compositions described herein. In one particular form,the metal oxide is selected from the group consisting of zinc oxide,ferric oxide, cupric oxide, titanium dioxide and mixtures thereof.

The metal oxide is typically present within the composition of thisembodiment in an activity enhancing amount. An activity enhancing amountis an amount which increases the half life of the composition, oralternatively will enable the composition to achieve the same control ofpests at a level which is less than the amount required for the samepesticidal protection or control of the composition in the absence ofthe metal oxide. In other words, the metal oxide will either reduce therate required for protection or extend the residuality of thecomposition.

In another embodiment, the at least one co-ingredient includes at leastone metal oxide and at least one proteinaceous material. It should beappreciated that the metal oxide in this embodiment can be one or amixture of those examples identified above. As used herein, the term“proteinaceous material” is used to describe a material, composition orcompound that is defined by a protein, includes at least one protein oris a basic element of a protein. In one form, the proteinaceous materialincludes a water-soluble protein. Further non-limiting examples ofproteinaceous materials include albumin, such as egg albumen or bovineserum albumin (BSA); casein; gelatin; zein; a whey composition, such asa mixture of lactose and whey protein; whey protein and amino acids suchas cysteine, methionine, trytophan, histidine, tyrosine, arginine,lysine, glutamine, glutamic acid, cystine, serine and asperigine, justto name a few possibilities. It is also contemplated that theco-ingredient could include two or more of the foregoing non-limitingexamples of the proteinaceous material. In one aspect of thisembodiment, the composition exhibits enhanced pesticidal activitycompared to a composition dissimilar only in not having the at least onemetal oxide and the at least one proteinaceous material.

The at least one metal oxide and the at least one proteinaceous materialare typically present within the composition of this embodiment in anactivity enhancing amount. An activity enhancing amount is an amountwhich increases the half life of the composition, or alternatively willenable the composition to achieve the same control of pests at a levelwhich is less than the amount required for the same pesticidalprotection or control of the composition in the absence of the metaloxide and the proteinaceous material. In other words, the metal oxideand the proteinaceous material will either reduce the rate required forprotection or extend the residuality of the composition.

In yet another embodiment, the at least one co-ingredient includes atleast one metal oxide and at least one polymeric material. In thisembodiment, it should be appreciated that the metal oxide can be one ormore of those examples identified above. As used herein, the term“polymeric material” is used to describe a material, compound orcomposition that is defined by or includes at least one polymer or aderivative thereof. In one non-limiting example, the polymeric materialincludes polyvinyl alcohol. In other examples, the polymeric materialmay include: a derivative of polyvinyl alcohol; polyvinyl pyrolidoneand/or one or more derivatives thereof; natural or synthetic latexes; apolysaccharide and/or one or more derivatives thereof, or polyvinylacetate and/or one or more derivatives thereof. In one specific example,the polymeric material may be a high molecular weight vinyl-acryliclatex, such as UCAR™ Latex 379G commercially available from The DowChemical Company, 2030 Dow Center, Midland, Mich. 48674. In anotherspecific example, the polymeric material may be a terpene polymer, suchas NU FILM 17® commercially available from Miller Chemical andFertilizer Corporation. P.O. Box 333, 120 Radio Road, Hanover, Pa.17331. In still another example, the polymeric material may be apolysaccharide or a modified polysaccharide such as starch, includingwater-soluble starches, potato starch and other processed starches,chitosan or methyl cellulose. In another example, the polymeric materialmay be a hypromellose polymer, such as METHOCEL™ K4M commerciallyavailable from The Dow Chemical Company. It should also be appreciatedthat the co-ingredient could include two or more of the foregoingnon-limiting examples of the polymeric material. In one aspect of thisembodiment, the composition exhibits enhanced pesticidal activitycompared to a composition dissimilar only in not having the at least onemetal oxide and the at least one polymeric material.

The at least one metal oxide and the at least one polymeric material aretypically present within the composition of this embodiment in anactivity enhancing amount. An activity enhancing amount is an amountwhich increases the half life of the composition, or alternatively willenable the composition to achieve the same control of pests at a levelwhich is less than the amount required for the same pesticidalprotection or control of the composition in the absence of the metaloxide and the polymeric material. In other words, the metal oxide andthe polymeric material will either reduce the rate required forprotection or extend the residuality of the composition.

In still another embodiment, the at least one co-ingredient includes atleast one metal oxide, at least one proteinaceous material and at leastone polymeric material. In this particular embodiment, it should beappreciated that the metal oxide, proteinaceous material and polymericmaterial can be one or more of those examples respectively identifiedabove for each. In one aspect of this embodiment, the compositionexhibits enhanced pesticidal activity compared to a compositiondissimilar only in not having the metal oxide, proteinaceous materialand polymeric material.

The at least one metal oxide, at least one proteinaceous material and atleast one polymeric material are typically present within thecomposition of this embodiment in an activity enhancing amount. Anactivity enhancing amount is an amount which increases the half life ofthe composition, or alternatively will enable the composition to achievethe same control of pests at a level which is less than the amountrequired for the same pesticidal protection or control of thecomposition in the absence of the metal oxide, proteinaceous materialand polymeric material. In other words, the metal oxide, proteinaceousmaterial and polymeric material will either reduce the rate required forprotection or extend the residuality of the composition.

In yet another embodiment, the at least one co-ingredient includes atleast one proteinaceous material and at least one polymeric material. Inthis particular embodiment, it should be appreciated that the at leastone proteinaceous material and the at least one polymeric material canbe one or more of those examples respectively identified above for each.In one aspect of this embodiment, the composition exhibits enhancedpesticidal activity compared to a composition dissimilar only in nothaving the proteinaceous material and the polymeric material.

The at least one proteinaceous material and the at least one polymericmaterial are typically present within the composition of this embodimentin an activity enhancing amount. An activity enhancing amount is anamount which increases the half life of the composition, oralternatively will enable the composition to achieve the same control ofpests at a level which is less than the amount required for the samepesticidal protection or control of the composition in the absence ofthe proteinaceous material and the polymeric material. In other words,the proteinaceous material and the polymeric material will either reducethe rate required for protection or extend the residuality of thecomposition.

In another embodiment, the at least one co-ingredient includes at leastone polymeric material. The polyermic material may be one or a mixtureof more than one of the polymeric materials described above and istypically present within the composition of this embodiment in anactivity enhancing amount. An activity enhancing amount is an amountwhich increases the half life of the composition, or alternatively willenable the composition to achieve the same control of pests at a levelwhich is less than the amount required for the same pesticidalprotection or control of the composition in the absence of the polymericmaterial. In other words, the polymeric material will either reduce therate required for protection or extend the residuality of thecomposition.

In still another embodiment, the at least one co-ingredient includes atleast one metal salt and at least one proteinaceous material. In thisembodiment, the composition exhibits enhanced pesticidal activitycompared to a composition dissimilar only in not having the metal saltand the proteinaceous material. As used herein, the term “metal salt”refers to a compound in which the hydrogen(s) of an acid is(are)replaced by a metal while retaining the same organic or inorganic moietyas the acid. By way of non-limiting example, organic and inorganicmoieties that can form part of a metal salt include acetate,acetylacetonate, nitrate, sulfate, carbonate and halides, such aschloride, bromide, fluoride and iodide.

In one or more forms, the metal salt can be a transition metal salt.Non-limiting examples of transition metal salts include transition metalacetates, transition metal acetylacetonates, transition metal nitrates,transition metal sulfates, transition metal carbonates and transitionmetal halides, including chlorides, fluorides, bromides and iodides.More particular examples of transition metal acetates include, but arenot limited to, zinc acetate, ferrous (iron (II)) acetate, ferric (iron(III)) acetate, cobalt (II) acetate and cupric (copper (II)) acetate.For transition metal acetylacetonates, more particular but non-limitingexamples include cuprous (copper (I)) acetylacetonate, cupric (copper(II)) acetylacetonate, nickel (II) acetylacetonate and zincacetylacetonate. More particular examples of transition metal nitratesinclude, but are not-limited to, zinc nitrate, cupric (copper (II))nitrate, manganese (II) nitrate, ferric (iron (III)) nitrate, cobalt(II) nitrate and nickel (II) nitrate. Non-limiting examples oftransition metal sulfates include zinc sulfate, ferrous (on (II))sulfate, ferric (iron (III)) sulfate, manganese (II) sulfate, cobalt(II) sulfate, nickel (II) sulfate, and cupric (copper (II)) sulfate. Afew particular but non-limiting examples of transition metal carbonatesinclude zinc carbonate, manganese (II) carbonate, iron carbonate, nickel(II) carbonate, cobalt (II) carbonate and cupric (copper (II))carbonate. More particular examples of transition metal fluoridesinclude, but are not limited to, cuprous (copper (I)) fluoride, cupric(copper (II)) fluoride, zinc fluoride, manganese (II) fluoride,manganese (III) fluoride and ferric (iron (III)) fluoride. Non-limitingexamples of transition metal chlorides include zinc chloride, cuprous(copper (I)) chloride, cupric (copper (II)) chloride, manganese (II)chloride, nickel (II) chloride, cobalt (II) chloride, ferrous (iron(II)) chloride and ferric (iron (III)) chloride. With respect totransition metal bromides, a few examples include, but are not limitedto, zinc bromide, cuprous (copper (I)) bromide, cupric (copper (II))bromide, cobalt (II) bromide, ferrous (iron (II)) bromide, ferric (iron(III)) bromide, manganese (II) bromide and nickel (II) bromide. A fewmore particular but non-limiting examples of transition metal iodidesinclude manganese (II) iodide, nickel (II) iodide, cuprous (copper (I))iodide and zinc iodide. Additionally, it is contemplated that the atleast one co-ingredient could include any combination of the abovetransition metal salts.

In another form of this embodiment, it is contemplated that the at leastone transition metal salt is water soluble. Non-limiting examples ofwater-soluble transition metal salts include zinc chloride, zinc iodide,zinc nitrate, zinc bromide, zinc sulfate, zinc acetate, cupric (copper(II)) chloride, cupric (copper II)) bromide, cuprous (copper (I))bromide, cupric (copper (II)) nitrate, cupric (copper (II)) acetate,nickel (II) nitrate, nickel (II) bromide, nickel (II) chloride, nickel(II) iodide, nickel (II) sulfate, cobalt (II) nitrate, cobalt (II)sulfate, cobalt (II) acetate, cobalt (II) bromide, cobalt (II) chloride,ferrous (iron (II)) chloride, ferric (iron (III)) chloride, ferrous(iron (II)) sulfate, ferric (iron (III)) sulfate, ferrous (iron (II))acetate, ferric (iron (III)) nitrate, ferrous (iron (II)) bromide,manganese (II) sulfate and manganese (II) chloride.

The at least one metal salt and the at least one proteinaceous materialare typically present within the composition of this embodiment in anactivity enhancing amount. An activity enhancing amount is an amountwhich increases the half life of the composition, or alternatively willenable the composition to achieve the same control of pests at a levelwhich is less than the amount required for the same pesticidalprotection or control of the composition in the absence of the metalsalt and the proteinaceous material. In other words, the metal salt andthe proteinaceous material will either reduce the rate required forprotection or extend the residuality of the composition.

Further details and examples of the above-described compositions may befound in U.S. patent application Ser. Nos. 12/768,057, 12/767,970, and12/768,084. each of which is entitled “PESTICIDE COMPOSITIONS EXHIBITINGENHANCED ACTIVITY” and was filed on the same date as the subjectapplication. The contents of each of these applications are herebyincorporated herein by reference in their entirety.

The compositions described above can be prepared and provided in anysuitable manner and also include other components, further details ofwhich will be provided below. In one exemplary form, the pesticide, theat least one co-ingredient that enhances the pesticidal activity of thepesticide, water and any other components, if present, are mixedtogether, homogenized and provided as a liquid composition. It has nowbeen surprisingly discovered that the liquid composition can be spraydried to provide a solid composition that exhibits enhanced pesticidalactivity relative to the liquid composition. The solid composition maybe in a powder or granular form, just to provide a few non-limitingpossibilities.

As will be appreciated by those skilled in the art, various parametersof the spray drying process, including feed rate, nozzle pressure, inlettemperature and outlet temperature amongst other possibilities, may beadjusted for each process performed. For example, in one non-limitingform, it is contemplated that a spray drying process may utilize a feedrate between about 200 and about 500 ml/hr, a nozzle pressure betweenabout 2 bar and about 8 bar, an inlet temperature between about 95° C.and about 180° C. and an outlet temperature between about 30° C. andabout 120° C. In another non-limiting form, it is contemplated that aspray drying process may utilize a feed rate between about 250 and about450 ml/hr, a nozzle pressure between about 3 bar and about 7 bar, aninlet temperature between about 105° C. and about 150° C. and an outlettemperature between about 40° C. and about 110° C. In yet anotherembodiment, it is contemplated that a spray drying process may utilize afeed rate from about 300 to about 400 ml/hr, a nozzle pressure fromabout 4 bar to about 6 bar, an inlet temperature from about 115° C. toabout 140° C. and an outlet temperature from about 50° C. to about 100°C. However, additional values for the feed rate, nozzle pressure, inlettemperature and outlet temperature at which the spray drying process isperformed are contemplated. Moreover, it should also be appreciated thatthe parameters utilized during the spray drying process will bedependent on the specific formulation of each composition and limited bythe upper and lower degradation limits of the ingredients included ineach composition being spray dried.

During the spray drying, the liquid composition is at least partiallydehydrated or dried, with such dehydration or dyring resulting in theconversion of the liquid composition to the solid composition whichincludes a smaller percentage by weight of water than the liquidcomposition. In one or more forms, the spray drying will remove all orsubstantially all of the water from the liquid composition as it isconverted to the solid composition. However, it should be appreciatedthat residual water may be present in one or more forms of the solidcomposition.

In one form, the spray drying reduces water from at least about 20% byweight in the liquid composition to less than about 15% by weight in thesolid composition. In yet another form, the spray drying reduces waterfrom at least about 40% by weight in the liquid composition to less thanabout 10% by weight in the solid composition. In still another form, thespray drying reduces water from at least about 50% by weight in theliquid composition to less than about 5% by weight in the solidcomposition. In another form, the spray drying reduces water from atleast about 50% by weight in the liquid composition to between about0.001% to about 2% by weight of water in the solid composition. Still,alternative values for the amount of water that is reduced from theliquid composition to the solid composition are contemplated. Forexample, in another form the spray drying reduces water from betweenabout 20% to about 90% by weight in the liquid composition to betweenabout 0.001 to about 15% by weight in the solid composition.

In another form, the solid composition includes between about 0.001% toabout 20% by weight of water after the spray drying. In yet anotherform, the solid composition includes from about 0.001% to about 15% byweight of water after the spray drying. In still another form, the solidcomposition includes from about 0.001% to about 10% by weight of waterafter the spray drying. In another form, the solid composition includesfrom about 0.001% to about 5% by weight of water after the spray drying.In yet another form, the solid composition includes from about 0.001% toabout 4% by weight of water after the spray drying. Still, in anotherform the solid composition includes from about 0.001% to about 2% byweight of water after the spray drying. In another form, the solidcomposition includes from about 0.001% to about 1% by weight of waterafter the spray drying. However, it should be appreciated thatalternatives values for the weight percentage of water in the solidcomposition after the spray drying are contemplated.

While not previously mentioned, any other volatile materials besideswater, if present in the liquid composition, will typically be entirelyor substantially removed as the liquid composition is converted to thesolid composition during the spray drying. However, it is contemplatedthat residual volatile materials other than water could be present inthe solid composition after the spray drying. Additionally, thepesticide and the at least one co-ingredient that enhances thepesticidal activity of the composition are generally not volatile andwill generally not be affected by the spray drying. Thus, it should beappreciated that the solid composition after spray drying will include aratio by weight between the pesticide and the at least one co-ingredientthat is the same as or substantially equivalent to the ratio by weightbetween the pesticide and the at least one co-ingredient in the liquidcomposition.

Pests

In one or more additional embodiments, the invention disclosed in thisdocument can be used to control pests.

In one embodiment, the invention disclosed in this document can be usedto control pests of the Phylum Nematoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Phylum Arthropoda. In another embodiment,the invention disclosed in this document can be used to control pests ofthe Subphylum Chelicerata.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Arachnida.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Myriapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Symphyla.

In another embodiment, the invention disclosed in this document can beused to control pests of the Subphylum Hexapoda.

In another embodiment, the invention disclosed in this document can beused to control pests of the Class Insecta.

In another embodiment, the invention disclosed in this document can beused to control Coleoptera (beetles). A non-exhaustive list of thesepests includes, but is not limited to, Acanthoscelides spp. (weevils),Acanthoscelides obtectus (common bean weevil), Agrilus planipennis(emerald ash borer), Agriotes spp. (wireworms Anoplophora glabripennis(Asian longhorned beetle), Anthonomus spp. (weevils), Anthonomus grandis(boll weevil), Aphidius spp., Apion spp. (weevils), Apogonia spp.(grubs), Ataenius spretulus (Black Turgrass Ataenius), Atomaria linearis(pygmy mangold beetle), Aulacophore spp., Bothynoderes punctiventris(beet root weevil), Bruchus spp. (weevils), Bruchus pisorum (peaweevil), Cacoesia spp., Callosobruchus maculatus (southern cow peaweevil), Carpophilus hemipteras (dried fruit beetle), Cassida vittata,Cerosterna spp., Cerotoma spp. (chrysomeids), Cerotoma trijiucata (beanleaf beetle), Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis(cabbage seedpod weevil), Ceutorhynchus napi (cabbage curculio),Chaetocnema spp. (chrysomelids), Colaspis spp. (soil beetles), Conoderusscalaris, Conoderus stigmosus, Conotrachelus nenuphar (plum curculio),Cotinus nitidis (Green June beetle), Crioceris asparagi (asparagusbeetle), Cryptolestes ferrugineus (rusty grain beetle), Cryptolestespusillus (flat grain beetle), Cryptolestes turcicus (Turkish gainbeetle), Ctenicera spp. (wireworms), Curculio spp. (weevils),Cyclocephala spp. (grubs), Cylindrocpturus adspersus (sunflower stemweevil), Deporaus marginatus (mango leaf-cutting weevil), Dermesteslardarius (larder beetle), Dermestes maculates (hide beetle), Diabroticaspp. (chrysolemids), Epilachna varivestis (Mexican bean beetle),Faustinus cubae, Hylobius pales (pales weevil), Hypera spp. (weevils),Hypera postica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cereal leafbeetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana, Phyllotreta spp.(chrysomelids), Phynchites spp., Popillia japonica (Japanese beetle),Prostephanus truncates (larger grain borer), Rhizopertha dominica(lesser grain borer), Rhizotrogus spp. (Eurpoean chafer), Rhynchophorusspp. (weevils), Scolytus spp. (wood beetles), Shenophorus spp.(Billbug), Sitona lineatus (pea leaf weevil), Sitophilus spp. (grainweevils), Sitophilus granaries (granary weevil), Sitophilus oryzae (riceweevil), Stegobium paniceum (drugstore beetle), Tribolium spp. (flourbeetles), Tribolium castaneum (red flour beetle), Tribolium confusum(confused flour beetle), Trogoderma variabile (warehouse beetle), andZabrus tenebioides.

In another embodiment, the invention disclosed in this document can beused to control Dermaptera (earwigs).

In another embodiment, the invention disclosed in this document can beused to control Dictyoptera (cockroaches). A non-exhaustive list ofthese pests includes, but is not limited to, Blattella germanica (Germancockroach), Blattaorientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In another embodiment, the invention disclosed in this document can beused to control Diptera (true flies). A non-exhaustive list of thesepests includes, but is not limited to, Aedes spp. (mosquitoes), Agromyzafrontella (alfalfa blotch leafminer), Agromyza spp. (leaf miner flies),Anastrepha spp. (fruit flies), Anastrepha suspensa (Caribbean fruitfly), Anopheles spp. (mosquitoes), Batrocera spp. (fruit flies),Bactrocera cucurbitae (melon fly), Bactrocera dorsalis (oriental fruitfly), Ceratitis spp. (fruit flies), Ceratitis capitata (Mediterraneafruit fly), Chrysops spp. (deer flies), Cochliomyia spp. (screwworms),Contarinia spp. (Gall midges), Culex spp. (mosquitoes), Dasineura spp.(gall midges), Dasineura brassicae (cabbage gall midge), Delia spp.,Delia platura (seedcorn maggot), Drosophila spp. (vinegar flies), Fanniaspp. (filth flies), Fannia canicularis (little house fly), Fanniascalaris (latrine fly), Gasterophilus intestinalis (horse bot fly),Gracillia perseae, Haematobia irritans (horn fly), Hylemyia spp. (rootmaggots), Hypoderma lineatum (common cattle grub), Liriomyza spp.(leafminer flies), Liriomyza brassica (serpentine leafminer), Melophagusovinus (sheep ked), Musca spp. (muscid flies), Musca autumnalis (facefly), Musca domestica (house fly), Oestrus ovis (sheep bot fly),Oscinella frit (frit fly), Pegomyia betae (beet leafminer), Phorbiaspp., Psila rosae (carrot rust fly), Rhagoletis cerasi (cherry fruitfly), Rhagoletis pomonella (apple maggot), Sitodiplosis mosellana(orange wheat blossom midge), Stomoxys calcitrans (stable fly), Tabanusspp. (horse flies), and Tipula spp. (crane flies).

In another embodiment, the invention disclosed in this document can beused to control Hemiptera (true bugs). A non-exhaustive list of thesepests includes, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Calocoris norvegicus (potatomind), Cimex hemipterus (tropical bed bug), Cimex lectularius (bed bug),Dagbertus fasciatus, Dichelops furcatus, Dysdercus suturellus (cottonstainer), Edessa meditabunda, Eurygaster maura (cereal bug), Euschistusheros, Euschistus servus (brown stink bug), Helopeltis antonii,Helopeltis theivora (tea blight plantbug), Lagynotomus spp. (stinkbugs), Leptocorisa oratorius, Leptocorisa varicornis, Lygus spp. (plantbugs), Lygus hesperus (western tarnished plant bug), Maconellicoccushirsutus, Neurocolpus longirostris, Nezara viridula (southern greenstink bug), Phytocoris spp. (plant bugs), Phytocoris californicus,Phytocoris relativus, Piezodorus guildingi, Poecilocapsus lineatus(fourlined plant bug), Psallus vaccinicola, Pseudacysta perseae,Scaptocoris castanea, and Triatoma spp. (bloodsucking conenosebugs/kissing bugs).

In another embodiment, the invention disclosed in this document can beused to control Homoptera (aphids, scales, whiteflies, leafhoppers). Anon-exhaustive list of these pests includes, but is not limited to,Acrythosiphon pisum (pea aphid), Adelges spp. (adelgids), Aleurodesproletella (cabbage whitefly), Aleurodicus disperses, Aleurothrixusfloccosus (woolly whitefly), Aluacaspis spp., Amrasca bigutellabigutella, Aphrophora spp. (leafhoppers), Aonidiella aurantii(California red scale), Aphis spp. (aphids), Aphis gossypii (cottonaphid), Aphis pomi (apple aphid), Aulacorthum solani (foxglove aphid),Bemisia spp. (whiteflies), Bemisia argentifolii, Bemisia tabaci(sweetpotato whitefly), Brachycolus noxius (Russian aphid),Brachycognella asparagi (asparagus aphid), Brevennia rehi, Brevicorynebrassicac (cabbage aphid), Ceroplastes spp. (scales), Ceroplastes rubens(red wax scale), Chionaspis spp. (scales), Chrysomphalus spp. (scales),Coccus spp. (scales), Dysaphis plantaginca (rosy apple aphid), Empoascaspp. (leafhoppers), Eriosoma lanigerum (woolly apple aphid), Iceryapurchasi (cottony cushion scale), Idioscopus nitidulus (mangoleafhopper), Laodelphax striatellus (smaller brown planthopper),Lepidosaphes spp., Macrosiphum spp., Macrosiphum euphorbiac (potatoaphid), Macrosiphum granarium (English grain aphid), Macrosiphum rosac(rose aphid), Macrosteles quadrilineatus (aster leafhopper), Mahanarvafrimbiolata, Metopolophium dirhodum (rose grain aphid), Mictislongicornis, Myzus persicae (green peach aphid), Nephotettix spp.(leafhoppers), Nephotettix cinctipes (green leafhopper), Nilaparvatalugens (brown planthopper), Parlatoria pergandii (chaff scale),Parlatoria ziziphi (ebony scale), Peregrinus maidis (corn delphacid),Philaenus spp. (spittlebugs), Phylloxera vittfoliae (grape phylloxera),Physokermes piceac (spruce bud scale), Planococcus spp. (mealybugs),Pseudococcus spp. (mealybugs), Pseudococcus brevipes (pine applemealybug), Quadraspidiotus perniciosus (San Jose scale), Rhapalosiphumspp. (aphids), Rhapalosiphum maida (corn leaf aphid), Rhapalosiphum padi(oat bird-cherry aphid), Saissetia spp. (scales), Saissetia oleae (blackscale), Schizaphis graminum (greenbug), Sitobion avenae (English grainaphid), Sogatella furcifera (white-backed planthopper), Therioaphis spp.(aphids), Toumeyella spp. (scales), Toxoptera spp. (aphids),Trialeurodes spp. (whiteflies), Trialeurodes vaporariorum (greenhousewhitefly), Trialeurodes abutiloneus (bandedwing whitefly), Unaspis spp.(scales), Unaspis yanonensis (arrowhead scale), and Zulia entreriana.

In another embodiment, the invention disclosed in this document can beused to control Hymenoptera (ants, wasps, and bees). A non-exhaustivelist of these pests includes, but is not limited to, Acromyrrmex spp.,Athalia rosae, Atta spp. (Ieafcutting ants), Camponotus spp. (carpenterants), Diprion spp. (sawflies), Formica spp. (ants), Iridomyrmex humilis(Argentine ant), Monomorium ssp., Monomorium minumum (little black ant),Monomorium pharaonis (Pharaoh ant), Neodiprion spp. (sawflies),Pogonomyrmex spp. (harvester ants), Polistes spp. (paper wasps),Solenopsis spp. (fire ants), Tapoinoma sessile (odorous house ant),Tetranomorium spp. (pavement ants), Vespula spp. (yellow jackets), andXylocopa spp. (carpenter bees).

In another embodiment, the invention disclosed in this document can beused to control Isoptera (termites). A non-exhaustive list of thesepests includes, but is not limited to, Coptotermes spp., Coptotermescurvignathus, Coptotermes frenchii, Coptoternzes formosanus (Formosansubterranean termite), Cornitermes spp. (nasute termites), Cryptotermesspp. (drywood termites), Heterotermes spp. (desert subterraneantermites), Heterotermes aureus, Kalotertnes spp. (drywood termites).Incistitermes spp. (drywood termites), Macrotermes spp. (fungus growingtermites), Marginitermes spp. (drywood termites), Microcerotermes spp.(harvester termites), Microtermes obesi, Procornitermes spp.,Reticulitermes spp. (subterranean termites), Reticulitermes banyulensis,Reticulitermes grassei, Reticulitermes flavipes (eastern subterraneantermite), Reticulitermes hageni, Reticulitermes hesperus (westernsubterranean termite), Reticulitermes santonensis, Reticulitermessperatus, Reticulitermes tibialis, Reticulitermes virginicus,Schedorhinotermes spp., and Zootermopsis spp. (rotten-wood termites).

In another embodiment, the invention disclosed in this document can beused to control Lepidoptera (moths and butterflies). A non-exhaustivelist of these pests includes, but is not limited to, Achoea janata,Adoxophyes spp., Adoxophyes orana, Agrotis spp. (cutworms), Agrotisipsilon (black cutworm), Alabama argillacea (cotton leafworm), Amorbiacuneana, Amyelosis transitella (navel orangeworm), Anacamptodesdefectaria, Anarsia lincatella (peach twig borer), Anomis sabulijera(jute looper), Anticarsia gemmatalis (velvetbean caterpillar), Archipsargyrospila (fruit tree leafroller), Archips rosana (rose leaf roller),Argyrotaenia spp. (tortricid moths), Argyrotaenia citrana (orangetortrix), Autographa gamma, Bonagota cranaodes, Borba cinnara (rice leaffolder), Bucculatrix thurberiella (cotton leaf perforator), Caloptiliaspp. (leaf miners), Capua reticulana, Carposina niponensis (peach fruitmoth), Chilo spp., Chlumetia transversa (mango shoot borer),Choristoneura rosaceana (oblique banded leaf roller), Chrysodeixis spp.,Cnaphalocerus medinalis (pass leafroller), Colias spp., Conpomorphacramerella, Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydia funebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraca saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobacco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma Salida (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonotycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarpa, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth).

In another embodiment, the invention disclosed in this document can beused to control Mallophaga (chewing lice). A non-exhaustive list ofthese pests includes, but is not limited to, Bovicola ovis (sheep bitinglouse), Menacanthus stramineus (chicken body louse), and Menopongallinea (common hen house).

In another embodiment, the invention disclosed in this document can beused to control Orthoptera (grasshoppers, locusts, and crickets). Anon-exhaustive list of these pests includes, but is not limited to,Anabrus simplex (Mormon cricket), Gryllotalpidae (mole crickets),Locusta migratoria, Melanoplus spp. (grasshoppers), Microcentrumretinerve (angular winged katydid), Pterophylla spp. (kaydids),chistocerca gregaria, Scudderia furcata (fork tailed bush katydid), andValanga nigricorni.

In another embodiment, the invention disclosed in this document can beused to control Phthiraptera (sucking lice). A non-exhaustive list ofthese pests includes, but is not limited to, Haematopinus spp. (cattleand hog lice), Linognathus ovillus (sheep louse), Pediculus humanuscapitis (human body louse), Pediculus humanus humanus (human body lice),and Pthirus pubis (crab louse).

In another embodiment, the invention disclosed in this document can beused to control Siphonaptera (fleas). A non-exhaustive list of thesepests includes, but is not limited to, Ctenocephalides canis (dog flea),Ctenocephalides felis (cat flea), and Pulex irritans (human flea).

In another embodiment, the invention disclosed in this document can beused to control Thysanoptera (thrips). A non-exhaustive list of thesepests includes, but is not limited to, Frankliniella fusca (tobaccothrips), Frankliniella occidentalis (western flower thrips),Frankliniella shultzei Frankliniella williamsi (corn thrips),Heliothrips haemorrhaidalis (greenhouse thrips), Riphiphorothripscruentatus, Scirtothrips spp., Scirtothrips citri (citrus thrips),Scirtothrips dorsalis (yellow tea thrips), Taeniothripsrhopalantennalis, and Thrips spp.

In another embodiment, the invention disclosed in this document can beused to control Thysanura (bristletails). A non-exhaustive list of thesepests includes, but is not limited to, Lepisma spp. (silverfish) andThermobia spp. (firebrats).

In another embodiment, the invention disclosed in this document can beused to control Acarina (mites and ticks). A non-exhaustive list ofthese pests includes, but is not limited to, Acarapsis woodi (trachealmite of honeybees), Acarus spp. (food mites), Acarus siro (grain mite),Acoria mangiferae (mango bud mite), Aculops spp., Aculops lycopersici(tomato russet mite), Aculops pelekasi, Acultis pelekassi, Aculusschlechtendali (apple rust mite), Amblyomma americanum (lone star tick),Boophilus spp. (ticks), Brevipalpus obovatus (privet mite), Brevipalpusphoenicis (red and black flat mite), Demodex spp. (mange mites),Dermacentor spp. (hard ticks), Dermacentor variabilis (american dogtick), Dermatophagoides pteronyssinus (house dust mite), Eotetranycusspp., Eotetranychus carpini (yellow spider mite), Epitimerus spp.,Eriophyes spp., Ixodes spp. (ticks), Metatetranycus spp., Notoedrescati, Oligonychus spp., Oligonychus coffee, Oligonychus ilicus (southernred mite), Panonychus spp., Panonychus citri (citrus red mite),Panonychus ulmi (European red mite), Phyllocoptruta oleivora (citrusrust mite), Polyphagotarsonemun latus (broad mite), Rhipicephalussanguineus (brown dog tick), Rhizoglyphus spp. (bulb mites), Sarcoptesscabiei (itch mite), Tegolophus persea, Tetranychus spp., Tetranychusurticae (twospotted spider mite), and Varroa destructor (honey beemite).

In another embodiment, the invention disclosed in this document can beused to control Nematoda (nematodes). A non-exhaustive list of thesepests includes, but is not limited to, Aphelenchoides spp. (bud and leaf& pine wood nematodes), Belonolaimus spp. (sting nematodes),Criconemella spp. (ring nematodes), Dirofilaria immitis (dog heartworm),Ditylenchus spp. (stem and bulb nematodes), Heterodera spp. (cystnematodes), Heterodera zeae (corn cyst nematode), Hirschmanniella spp.(root nematodes), Hoplolalimus spp. (lance nematodes), Meloidogyne spp.(root knot nematodes), Meloidogyne incognita (root knot nematode),Onchocerca volvulus (hook-tail worm), Pratylenchus spp. (lesionnematodes), Radopholus spp. (burrowing nematodes), and Rotylenchusreniformis (kidney-shaped nematode).

In another embodiment, the invention disclosed in this document can beused to control Symphyla (symphylans). A non-exhaustive list of thesepests includes, but is not limited to, Scutigerella immaculata.

For more detailed information consult “HANDBOOK OF PEST CONTROL—THEBEHAVIOR, LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by ArnoldMollis, 9th Edition, copyright 2004 by GIE Media Inc.

Mixtures

The compositions disclosed in this document can also be used, forreasons of economy and synergy, with acaricides, algicides,antifeedants, avicides, bactericides, bird repellents, chemosterilants,fungicides, herbicide safeners, herbicides, insect attractants, insectrepellents, mammal repellents, mating disrupters, molluscicides, otherinsecticides, other pesticides, plant activators, plant growthregulators, rodenticides, synergists, defoliants, desiccants,disinfectants, semiochemicals, and virucides (these categories notnecessarily mutually exclusive).

Formulations

The compositions described in this document may also be provided with aphytologically-acceptable inert carrier and can be formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra low volume solutions.

For further information on formulation types see “CATALOGUE OF PESTICIDEFORMULATION TYPES AND INTERNATIONAL CODING SYSTEM” Technical Monographn°2, 5th Edition by Crop Life International (2002).

Pesticide compositions can be frequently applied as aqueous suspensionsor emulsions prepared from concentrated formulations of suchcompositions. Such water-soluble, water-suspendable, or emulsifiableformulations are either solids, usually known as wettable powders, orwater dispersible granules, or liquids usually known as emulsifiableconcentrates, or aqueous suspensions. Wettable powders, which may becompacted to form water dispersible granules, comprise an intimatemixture of the pesticide composition, a carrier, and surfactants. Thecarrier is usually chosen from among the attapulgite clays, themontmorillonite clays, the diatomaceous earths, or the purifiedsilicates. Effective surfactants, which can comprise from about 0.5% toabout 10% of the wettable powder, are found among sulfonated lignins,condensed naphthalenesulfonates, naphthalenesulfonates,alkylbenzenesulfonates, alkyl sulfates, and nonionic surfactants such asethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates comprise a convenient concentration of apesticide composition dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are chosen from conventionalanionic and nonionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidecompositions dispersed in an aqueous carrier. Suspensions are preparedby finely grinding the pesticide composition and vigorously mixing itinto a carrier comprised of water and surfactants. Ingredients, such asinorganic salts and synthetic or natural gums, may also be added, toincrease the density and viscosity of the aqueous carrier. It is oftenmost effective to grind and mix the pesticide composition at the sametime by preparing the aqueous mixture and homogenizing it in animplement such as a sand mill, ball mill, or piston-type homogenizer.

Pesticide compositions may also be applied as granular formulations thatare particularly useful for applications to the soil. Granularformulations contain the pesticide composition dispersed in a carrierthat comprises clay or a similar substance. Such formulations areusually prepared by dissolving the pesticide composition in a suitablesolvent and applying it to a granular carrier which has been pre-formedto the appropriate particle size, in the range of from about 0.5 to 3mm. Such formulations may also be formulated by making a dough or pasteof the carrier and pesticide composition and crushing and drying toobtain the desired granular particle size.

Dusts containing a pesticide composition are prepared by intimatelymixing the pesticide composition in powdered form with a suitable dustyagricultural carrier, such as kaolin clay, ground volcanic rock, and thelike. Dusts can be applied as a seed dressing, or as a foliageapplication with a dust blower machine.

It is equally practical to apply a pesticide composition in the form ofa solution in an appropriate organic solvent, usually petroleum oil,such as the spray oils, which are widely used in agricultural chemistry.

Pesticide compositions can also be applied in the form of an aerosolformulation. In such formulations, the pesticide composition isdissolved or dispersed in a carrier, which is a pressure-generatingpropellant mixture. The aerosol formulation is packaged in a containerfrom which the mixture is dispensed through an atomizing valve.

Pesticide baits are formed when the pesticide composition is mixed withfood or an attractant or both. When the pests eat the bait they alsoconsume the pesticide composition. Baits may take the form of granules,gels, flowable powders, liquids, or solids. They may be used in oraround pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings or in special chambers.

Oil solution concentrates are made by dissolving a pesticide compositionin a solvent that will hold the pesticide composition in solution. Oilsolutions of a pesticide composition usually provide faster knockdownand kill of pests than other formulations due to the solvents themselveshaving pesticidal action and the dissolution of the waxy covering of theintegument increasing the speed of uptake of the pesticide. Otheradvantages of oil solutions include better storage stability, betterpenetration of crevices, and better adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one compound which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers. Further information onthe embodiment is disclosed in U.S. patent publication 20070027034published Feb. 1, 2007, having patent application Ser. No. 11/495,228.For ease of use this embodiment will be referred to as “OIWE”.

For further information consult “INSECT PEST MANAGEMENT” 2nd Edition byD. Dent, copyright CAB International (2000). Additionally, for moredetailed information consult “HANDBOOK OF PEST CONTROL—THE BEHAVIOR,LIFE HISTORY, AND CONTROL OF HOUSEHOLD PESTS” by Arnold Mallis, 9thEdition, copyright 2004 by GIE Media Inc.

Other Formulation Components

Generally, when the compositions disclosed in this document are used ina formulation, such formulation can also contain other components. Thesecomponents include, but are not limited to, (this is a non-exhaustiveand non-mutually exclusive list) wetters, spreaders, stickers,penetrants, buffers, sequestering agents, drift reduction agents,compatibility agents, anti-foam agents, cleaning agents, andemulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulphate;sodium dioctyl sulphosuccinate; alkyl phenol ethoxylates; and aliphaticalcohol ethoxylates.

A dispersing agent is a substance which adsorbs onto the surface ofparticles and helps to preserve the state of dispersion of the particlesand prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulphonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such as sodium naphthalene sulphonate formaldehydecondensates. Tristyrylphenol ethoxylate phosphate esters are also used.Non-ionics such as alkylarylethylene oxide condensates and EO-PO blockcopolymers are sometimes combined with anionics as dispersing agents forsuspension concentrates. In recent years, new types of very highmolecular weight polymeric surfactants have been developed as dispersingagents. These have very long hydrophobic ‘backbones’ and a large numberof ethylene oxide chains forming the ‘teeth’ of a ‘comb’ surfactant.These high molecular weight polymers can give very good long-termstability to suspension concentrates because the hydrophobic backboneshave many anchoring points onto the particle surfaces. Examples ofdispersing agents used in agrochemical formulations are: sodiumlignosulphonates; sodium naphthalene sulphonate formaldehydecondensates; tristyrylphenol ethoxylate phosphate esters; aliphaticalcohol ethoxylates; alky ethoxylates; EO-PO block copolymers; and graftcopolymers.

An emulsifying agent is a substance which stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends containalkylphenol or aliphatic alcohol with 12 or more ethylene oxide unitsand the oil-soluble calcium salt of dodecylbenzene sulphonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from 8 to 18 willnormally provide good stable emulsions. Emulsion stability can sometimesbe improved b the addition of a small amount of an EO-PO block copolymersurfactant.

A solubilizing agent is a surfactant which will form micelles in waterat concentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics: sorbitan monooleates; sorbitanmonooleate ethoxylates; and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alky ethoxylates; linear aliphatic alcoholethoxylates; aliphatic amine ethoxylates.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, ULV formulations, and to a lesser extent granularformulations. Sometimes mixtures of solvents are used. The first maingroups of solvents are aliphatic paraffinic oils such as kerosene orrefined paraffins. The second main group and the most common comprisesthe aromatic solvents such as xylene and higher molecular weightfractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons areuseful as cosolvents to prevent crystallization of pesticides when theformulation is emulsified into water. Alcohols are sometimes used ascosolvents to increase solvent power.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, emulsions and suspoemulsions to modify therheology or flow properties of the liquid and to prevent separation andsettling of the dispersed particles or droplets. Thickening, gelling,and anti-settling agents generally fall into two categories, namelywater-insoluble particulates and water-soluble polymers. It is possibleto produce suspension concentrate formulations using clays and silicas.Examples of these types of materials, include, but are limited to,montmorillonite, e.g. bentonite; magnesium aluminum silicate; andattapulgite. Water-soluble polysaccharides have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum; locust bean gum; carrageenam;alginates; methyl cellulose; sodium carboxymethyl cellulose (SCMC);hydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms cause spoilage of formulated products. Thereforepreservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt; sorbic acid and its sodium or potassium salts;benzoic acid and its sodium salt; p-hydroxy benzoic acid sodium salt;methyl p-hydroxy benzoate; and 1,2-benzisothiazalin-3-one (BIT).

The presence of surfactants, which lower interfacial tension, oftencauses water-based formulations to foam during mixing operations inproduction and in application through a spray tank. In order to reducethe tendency to foam, anti-foam agents are often added either during theproduction stage or before filling into bottles. Generally, there aretwo types of anti-foam agents, namely silicones and non-silicones.Silicones are usually aqueous emulsions of dimethyl polysiloxane whilethe non-silicone anti-foam agents are water-insoluble oils, such asoctanol and nonanol, or silica. In both cases, the function of theanti-foam agent is to displace the surfactant from the air-waterinterface.

For further information see “CHEMISTRY AND TECHNOLOGY OF AGROCHEMICALFORMULATIONS” edited by D. A. Knowles, copyright 1998 by Kluwer AcademicPublishers. Also see “INSECTICIDES IN AGRICULTURE ANDENVIRONMENT—RETROSPECTS AND PROSPECTS” by A. S. Perry, Yamamoto, I.Ishaaya, and R. Perry, copyright 1998 by Springer-Verlag.

Applications

The actual amount of a pesticide composition to be applied to loci ofpests is generally not critical and can readily be determined by thoseskilled in the art. In general, concentrations from about 0.01 grams ofpesticide per hectare to about 5000 grams of pesticide per hectare areexpected to provide good control.

The locus to which a pesticide composition is applied can be any locusinhabited by a pest, for example, vegetable crops, fruit and nut trees,grape vines, ornamental plants, domesticated animals, the interior orexterior surfaces of buildings, and the soil around buildings.Controlling pests generally means that pest populations, activity, orboth, are reduced in a locus. This can come about when: pest populationsare repulsed from a locus; when pests are incapacitated in or around alocus; or pests are exterminated, in whole or in part, in or around alocus. Of course a combination of these results can occur. Generally,pest populations, activity, or both are desirably reduced more thanfifty percent, preferably more than 90 percent.

Generally, with baits, the baits are placed in the ground where, forexample, termites can come into contact with the bait. Baits can also beapplied to a surface of a building, (horizontal, vertical, or slanted,surface) where, for example, ants, termites, cockroaches, and flies, cancome into contact with the bait.

Because of the unique ability of the eggs of some pests to resistpesticide compositions repeated applications may be desirable to controlnewly emerged larvae.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying the pesticide compositionto a different portion of the plant. For example, control offoliar-feeding insects can be controlled by drip irrigation or furrowapplication, or by treating the seed before planting. Seed treatment canbe applied to all types of seeds, including those from which plantsgenetically transformed to express specialized traits will germinate.Representative examples include those expressing proteins toxic toinvertebrate pests, such Bacillus thuringiensis or other insecticidaltoxins, those expressing herbicide resistance, such as “Roundup Ready”seed, or those with “stacked” foreign genes expressing insecticidaltoxins, herbicide resistance, nutrition-enhancement or any otherbeneficial traits. Furthermore, such seed treatments with the inventiondisclosed in this document can further enhance the ability of a plant tobetter withstand stressful growing conditions. This results in ahealthier, more vigorous plant, which can lead to higher yields atharvest time.

It should be readily apparent that the invention can be used with plantsgenetically transformed to express specialized traits, such as Bacillusthuringiensis or other insecticidal toxins, or those expressingherbicide resistance, or those with “stacked” foreign genes expressinginsecticidal toxins, herbicide resistance, nutrition-enhancement or anyother beneficial traits.

The invention disclosed in this document is suitable for controllingendoparasites and ectoparasites in the veterinary medicine sector or inthe field of animal keeping. Compositions are applied in a known manner,such as by oral administration in the form of, for example, tablets,capsules, drinks, granules, by dermal application in the form of, forexample, dipping, spraying, pouring on, spotting on, and dusting, and byparenteral administration in the form of for example, an injection.

The invention disclosed in this document can also be employedadvantageously in livestock keeping, for example, cattle, sheep, pigs,chickens, and geese. Suitable formulations are administered orally tothe animals with the drinking water or feed. The dosages andformulations that are suitable depend on the species.

Before a pesticide composition can be used or sold commercially, suchcomposition undergoes lengthy evaluation processes by variousgovernmental authorities (local, regional, state, national,international). Voluminous data requirements are specified by regulatoryauthorities and must be addressed through data generation and submissionby the product registrant or by another on the product registrant'sbehalf These governmental authorities then review such data and if adetermination of safety is concluded, provide the potential user orseller with product registration approval. Thereafter, in that localitywhere the product egistration is granted and supported, such user orseller may use or sell such pesticide.

EXAMPLES

The following examples are for illustration purposes and are not to beconstrued as limiting the invention disclosed in this document to onlythe embodiments disclosed in these examples.

Example Compositions

Example compositions A-H described below each include spinetoram.Spinetoram is a mixture of 50-90%(2R,3aR,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-3-O-ethyl-2,4-di-O-methyl-α-L-mannopyranosyloxy)-13-[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methylpyran-2-yloxy]-9-ethyl-2,3,3a,4,5,5a,5b,6,9,10,11,12,13,14,16a,16b-hexadecahydro-14-methyl-1H-as-indaceno[3,2-d]oxacyclododecine-7,15-dioneand 50-10%(2R,3aR,5aS,5bS,9S,13S,14R,16aS,16bS)-2-(6-deoxy-3-O-ethyl-2,4-di-O-methyl-α-L-mannopyranosyloxy)-13-[(2R,5S,6R)-5-(dimethylamino)tetrahydro-6-methylpyran-2-yloxy]-9-ethyl-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-tetradecahydro-4,14-dimethyl-1H-as-indaceno[3,2-d]oxacyclododecine-7,15-dione.Spinetoram is synthetically derived from a natural product and istypically accompanied by various impurities. Accordingly, for each ofthe compositions prepared below in Examples A-H, an assay was performedon the spinetoram used to determine the presence of impurities. For eachassay a calibration stock solution sample was prepared by addingapproximately 43 mg of an analytically standard form of spinetoram with10.0 mL of purified water into a 125 mL glass jar. The glass jar wasgently swirled until the spinetoram was dispersed into the purifiedwater. 100.0 mL of methanol was then added to the water/spinetorammixture in the glass jar. A second solution was prepared by adding 10 mLof purified water and approximately 50 mg of the spinetoram product usedin each of Examples A-H to a 125 mL glass jar. The glass jar was gentlyswirled until the spinetoram dispersed into the purified water. 100.0 mLof methanol was then added to the mixture. Each sample was then analyzedusing liquid chromatography performed with the following instrumentationand under the following conditions:

Chromatograph: Agilent (formally Hewlett Packard) model 1100 orequivalent Column: Phenomenex Luna, C8(2) 3 μm, 150 m × 4.6 mm columnMobile Phase A: water with 2 g/L ammonium acetate, pH adjusted to 5.5with acetic acid Mobile Phase B: acetonitrile/methanol (80:20, v:v)Isocratic elution: 20% A/80% B Flow: 1.0 mL/minute Injection volume:10.0 μL Detector: UV @ 250 nm Run Time: 20 minutes Integrator: AgilentEZChrom Elite data acquisition system, or equivalentBased on the results of the liquid chromatography, the weight percentageof the pure spinetoram component of each of the spinetoram products usedin Examples A-H was calculated. The weight percentage of impurities wasthen calculated by subtracting the weight percentage of the purespinetoram component from 100. The weight percentage of spinetoramimpurities in each of Examples A-H, based from these calculations, isprovided below.

Example A

A liquid composition including spinetoram, zinc oxide and egg albumen,among other ingredients, was prepared according to the following.Spinetoram, Reax® 88A, a dispersant commercially available fromMeadWestvaco Corporation, P.O. Box 118005, Charleston, S.C. 29423,Geropon® SDS, a surfactant commercially available from Rhodia, Inc., 8Cedar Brook Drive, Cranbury, N.J. 08512 and a balance of water toprovide a suspension concentrate having 25-50% w/w of spinetoram weremixed together. The resulting mixture was milled in an Eiger MiniMotormill media mill to a particle size of 1-10 μm (volume weighted meandiameter). The particle size was measured using a Malvern Mastersizer2000 laser diffraction particle analyzer. After milling, Nanox® 500, azinc oxide product commercially available from Elementis Specialties,Inc., P.O. Box 700, 329 Wyckoffs Mill Road, Hightstown, N.J. 08520, andegg albumen from Grade II chicken egg whites from Sigma AldrichCorporation, 3050 Spruce St., St. Louis, Mo. 63103, were added to themixture under agitation. The total solids concentration of the mixturewas adjusted in the range of 20-50% by weight by adding water. Themixture was then homogenized with a Silverson L4RT-A homogenizer forabout 15-30 minutes. The weight percentages for the foregoingingredients, calculated by comparing the weight of each respectiveingredient relative to the total weight of the liquid composition, areprovided in Table 1. Table 1 also provides the weight percentage ofspinetoram impurities in the liquid composition based on the valuesdetermined by the assay procedure described above.

TABLE 1 Example A Ingredients Wt. % Spinetoram 3.11 Spinetoramimpurities 0.64 Egg Albumen 15.86 ZnO 10.09 Reax ® 88A 1.13 Geropon ®SDS 0.23 Water 68.94

The liquid composition of Example A was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram so appropriate concentrationsfor testing could be prepared. For this assay procedure, a calibrationstock solution sample was prepared by adding approximately 43 mg of ananalytically standard form of spinetoram with 10.0 mL of purified waterinto a 125 mL glass jar. The glass jar was gently swirled until thespinetoram was dispersed into the purified water. 100.0 mL of methanolwas then added to the water/spinetoram mixture in the glass jar. Asecond solution was prepared by adding 10 mL of purified water andapproximately 130 mg of the liquid composition to a 125 mL glass jar.The glass jar was gently swirled until the composition dispersed intothe purified water. 100.0 mL of methanol was then added to the mixtureand the mixture was shaken for at least about 5 minutes on a mechanicalshaker. An aliquot of the mixture was then filtered through a 0.45 μmnylon syringe filter, with the first few filtered drops being discarded,and the remaining filtrate providing a sample for liquid chromatography.Each sample was then analyzed using liquid chromatography performed withthe following instrumentation and under the following conditions:

Chromatograph: Agilent (formally Hewlett Packard) model 1100 orequivalent Column: Phenomenex Luna, C8(2) 3 μm, 150 m × 4.6 mm columnMobile Phase A: water with 2 g/L ammonium acetate, pH adjusted to 5.5with acetic acid Mobile Phase B: acetonitrile/methanol (80:20, v:v)Isocratic elution: 20% A/80% B Flow: 1.0 mL/minute Injection volume:10.0 μL Detector: UV @ 250 nm Run Time: 20 minutes Integrator: AgilentEZChrom Elite data acquisition system, or equivalent

Based on the results of the liquid chromatography, the weight percentageof the pure spinetoram component for the liquid composition of Example Awas calculated to be 3.1%.

Example B

A portion of the liquid composition prepared in Example A wasspray-dried using a Buchi® Model 190 bench top spray dryer from BuchiCorporation, 19 Lukens Drive, Suite 400, New Castle, Del. 19720, atabout a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure, 115-140° C.inlet temperature and 50-100° C. outlet temperature to provide Example Bas a solid composition. It is believed that the spray drying processremoves all or substantially all of the water and other volatileingredients from the liquid composition of Example A as it is convertedto the solid composition of Example B. Since none of the ingredients inthe liquid composition of Example A apart from the water is believed tobe volatile, the weight percentages for each of the ingredients in thesolid composition of Example B were determined on the basis of all waterbeing removed from the liquid composition of Example A during the spraydrying. These weight percentages are set forth in Table 2.

TABLE 2 Example B Ingredients Wt. % Spinetoram 10.0 Spinetoramimpurities 2.05 Egg Albumen 51.08 ZnO 32.5 Reax ® 88A 3.64 Geropon ® SDS0.73

Since the solid composition of Example B was later used for bio-efficacyexperiments, an assay was performed to determine its proportion byweight of pure spinetoram so appropriate concentrations for testingcould be prepared. For this assay procedure, a calibration stocksolution sample was prepared by adding approximately 43 mg of ananalytically standard form of spinetoram with 10.0 mL of purified waterinto a 125 mL glass jar. The glass jar was gently swirled until thespinetoram was dispersed into the purified water. 100.0 mL of methanolwas then added to the water/spinetoram mixture in the glass jar. Asecond solution was prepared by adding 10 mL of purified water andapproximately 130 mg of the solid composition of Example B to a 125 mLglass jar. The glass jar was gently swirled until the solid compositiondispersed into the purified water. 100.0 mL of methanol was then addedto the mixture and the mixture was shaken for at least about 5 minuteson a mechanical shaker. An aliquot of the mixture was then filteredthrough a 0.45 μm nylon syringe filter, with the first few filtereddrops being discarded, and the remaining filtrate providing a sample forliquid chromatography. Each sample was then analyzed using liquidchromatography performed with the instrumentation and in accordance withthe parameters set forth above in Example A. Based on the results of theliquid chromatography, the weight percentage of the pure spinetoramcomponent for the solid composition of Example B was calculated to be

Example C

A liquid composition including spinetoram, egg albumen and polyvinylalcohol, among other ingredients, was prepared according to thefollowing. Spinetoram, Reax® 88A, Geropon® SDS and a balance of water toprovide a suspension concentrate having 25-50% w/w of spinetoram weremixed together. The resulting mixture was milled in an Eiger MiniMotormill media mill from Eiger Machinery, Inc. to a particle size of1-10 μm (volume weighted mean diameter). The particle size was measuredusing a Malvern Mastersizer 2000 laser diffraction particle analyzerfrom Malvern Instruments Ltd. After milling, egg albumen from Grade IIchicken egg whites from Sigma Aldrich Corporation and a 15% w/w aqueoussolution of Celvol® 205 polyvinyl alcohol from Celanese Corporation,1601 West LBJ Freeway, Dallas, Tex., 75234, were added to the mixtureunder agitation. The 15% w/w aqueous solution of Celvol® 205 polyvinylalcohol was prepared according to manufacturer instructions. The totalsolids concentration of the mixture was adjusted in the range of 20-50%by weight by adding water. The mixture was then homogenized with aSilverson L4RT-A homogenizer from Silverson Machines Inc. for about15-30 minutes. The weight percentages for the foregoing ingredients,calculated by comparing the weight of each respective ingredientrelative to the total weight of the liquid composition, are provided inTable 3. Table 3 also provides the weight percentage of spinetoramimpurities in the liquid composition based on the values determined bythe assay procedure described above.

TABLE 3 Example C Ingredients Wt. % Spinetoram 4.0 Spinetoram impurities0.8 Egg Albumen 28.22 Celvol ® 205 6.4 Reax ® 88A 0.48 Geropon ® SDS 0.1Water 60.0

The liquid composition of Example C was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram so appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example A and the weightpercentage of the pure spinetoram component for the liquid compositionwas calculated to be 4.0%.

Example D

A portion of the liquid composition prepared in Example C wasspray-dried using a Buchi® Model 190 bench top spray dryer from BuchiCorporation at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure,115-140° C. inlet temperature and 50-100° C. outlet temperature toprovide Example D as a solid composition. It is believed that the spraydrying process removes all or substantially all of the water and othervolatile ingredients from the liquid composition of Example C as it isconverted to the solid composition of Example D. Since none of theingredients in the liquid composition of Example C apart from the wateris believed to be volatile, the weight percentages for each of theingredients in the solid composition of Example D were determined on thebasis of all water being removed from the liquid composition of ExampleC during the spray drying. These weight percentages are set forth inTable 4.

TABLE 4 Example D Ingredients Wt. % Spinetoram 10.0 Spinetoramimpurities 2.0 Egg Albumen 70.56 Celvol ® 205 16.0 Reax ® 88A 1.2Geropon ® SDS 0.24

The solid composition of Example D was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram no appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example B and the weightpercentage of the pure spinetoram component for the powder compositionof Example D was calculated to be 9.6%.

Example E

A liquid composition including spinetoram, iron (III) oxide and apolyvinyl pyrolidone product, among other ingredients, was preparedaccording to the following. Spinetoram, Kraftsperse® 25M, a dispersantcommercially available from MeadWestvaco Corporation, P.O. Box 118005,Charleston, S.C. 29423, Soprophor® 3D33, a surfactant commerciallyavailable from Rhodia, Inc., 8 Cedar Brook Drive, Cranbury, N.J. 08512,Dow Corning® 200, an anti-foaming agent commercially available from DowCorning Corporation, P.O. Box 994, Midland, Mich. 48686, Proxel® GXL, amicrobiostat solution commercially available from Arch Chemicals, Inc.,1955 Lake Park Drive, Suite 100, Smyrna, Ga. 30080, and a balance ofwater to provide a suspension concentrate having 25-50% w/w ofspinetoram were mixed together. The resulting mixture was milled in anEiger Mini Motormill media mill to a particle size of 1-10 (volumeweighted mean diameter). The particle size was measured using a MalvernMastersizer 2000 laser diffraction particle analyzer. After milling,500M, an iron (III) oxide product commercially available from MagneticsInternational, Inc., Foster Plaza No. 7, 661 Andersen Drive, Pittsburgh,Pa. 15220, and a 5% w/w aqueous solution of Agrimer VA 6, a vinylpyrolidone/vinylacetate co-polymer at a 4:6 ratio, (lot #5600168453)commercially available from International Specialty Products, Inc., 1361Alps Road, Wayne, N.J. 07470, were added to the mixture under agitation.The 5% w/w aqueous solution of Agrimer VA 6 was prepared by mixingappropriate amounts of the Agrimer VA 6 with water. The total solidsconcentration of the mixture was adjusted in the range of 20-50% byweight by adding water. The mixture was then homogenized with aSilverson L4RT-A homogenizer for about 15-30 minutes. The weightpercentages for the foregoing ingredients, calculated by comparing theweight of each respective ingredient relative to the total weight of thecomposition, are provided in Table 5. Table 5 also provides the weightpercentage of spinetoram impurities in the composition based on thevalues determined by the assay procedure described above.

TABLE 5 Example E Ingredients Wt. % Spinetoram 7.18 Spinetoramimpurities 1.17 Fe₂O₃ 12.15 Agrimer VA 6 1.09 Kraftsperse ® 25M 1.17Soprophor ® 3D33 0.28 Dow Corning ® 200 0.03 Proxel ® GXL 0.02 Water76.91

The liquid composition of Example E was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram so appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example A and the weightpercentage of the pure spinetoram component for the liquid compositionwas calculated to be 6.2%.

Example F

A portion of the liquid composition prepared in Example E wasspray-dried using a Buchi® Model 190 bench top spray dryer from BuchiCorporation at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure,115-140° C. inlet temperature and 50-100° C. outlet temperature toprovide Example F as a solid composition. It is believed that the spraydrying process removes all or substantially all of the water and othervolatile ingredients from the liquid composition of Example E as it isconverted to the solid composition of Example F. Since none of theingredients in the liquid composition of Example E apart from the wateris believed to be volatile, the weight percentages for each of theingredients in the solid composition of Example F were determined on thebasis of all water being removed from the liquid composition of ExampleE during the spray drying.

These weight percentages are set forth in Table 6.

TABLE 6 Example F Ingredients Wt. % Spinetoram 31.1 Spinetoramimpurities 5.08 Fe₂O₃ 52.63 Agrimer VA 6 4.71 Kraftsperse ® 25M 5.06Soprophor ® 3D33 1.2 Dow Corning ® 200 0.14 Proxel ® GXL 0.08

The solid composition of Example F was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram so appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example B and the weightpercentage of the pure spinetoram component for the powder compositionof Example F was calculated to be 31.3%.

Example G

Another portion of the liquid composition prepared in Example E wasspray-dried using a Buchi® Model 190 bench top spray dryer from BuchiCorporation at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure,150° C. inlet temperature and 50-100° C. outlet temperature to provideExample G as a solid composition. It is believed that the spray dryingprocess removes all or substantially all of the water and other volatileingredients from the liquid composition of Example E as it is convertedto the solid composition of Example G. Since none of the ingredients inthe liquid composition of Example E apart from the water is believed tobe volatile, the weight percentages for each of the ingredients in thesolid composition of Example G were determined on the basis of all waterbeing removed from the liquid composition of Example E during the spraydrying. These weight percentages are set forth in Table 7.

TABLE 7 Example G Ingredients Wt. % Spinetoram 31.1 Spinetoramimpurities 5.08 Fe₂O₃ 52.63 Agrimer VA 6 4.71 Kraftsperse ® 25M 5.06Soprophor ® 3D33 1.2 Dow Corning ® 200 0.14 Proxel ® GXL 0.08

The solid composition of Example G was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram so appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example B and the weightpercentage of the pure spinetoram component for the powder compositionof Example G was calculated to be 34.57%.

Example H

Another portion of the liquid composition prepared in Example E wasspray-dried using a Buchi® Model 190 bench top spray dryer from BuchiCorporation at about a 300-400 ml/hr feed rate, 4-6 bar nozzle pressure,170° C. inlet temperature and 50-100° C. outlet temperature to provideExample H as a solid composition. It is believed that the spray dryingprocess removes all or substantially all of the water and other volatileingredients from the liquid composition of Example E as it is convertedto the solid composition of Example H. Since none of the ingredients inthe liquid composition of Example E apart from the water is believed tobe volatile, the weight percentages for each of the ingredients in thesolid composition of Example H were determined on the basis of all waterbeing removed from the liquid composition of Example E during the spraydrying. These weight percentages are set forth in Table 8.

TABLE 8 Example H Ingredients Wt. % Spinetoram 31.1 Spinetoramimpurities 5.08 Fe₂O₃ 52.63 Agrimer VA 6 4.71 Kraftsperse ® 25M 5.06Soprophor ® 3D33 1.2 Dow Corning ® 200 0.14 Proxel ® GXL 0.08

The solid composition of Example H was later used for bio-efficacyexperiments, but an assay was performed beforehand to determine itsproportion by weight of pure spinetoram an appropriate concentrationsfor testing could be prepared. The assay was performed according to theprocedure described above with respect to Example B and the weightpercentage of the pure spinetoram component for the powder compositionof Example H was calculated to be 35.33%.

As indicated above, the solid composition provided after spray dryingwill include a ratio by weight between the pesticide and the at leastone co-ingredient that is the same as or substantially equivalent to theratio by weight between the pesticide and the at least one co-ingredientin the liquid composition. For example, with respect to Examples A andB, Example A includes a 3.2:1 ratio by weight between zinc oxide andspinetoram, a 5.1:1 ratio by weight between egg albumen and spinetoramand a 1.6:1 ratio by weight between egg albumen and zinc oxide, whileExample B includes a 3.3:1 ratio by weight between zinc oxide andspinetoram, a 5.1:1 ratio by weight between egg albumen and spinetoramand a 1.6:1 ratio by weight between egg albumen and zinc oxide. Withrespect to Examples C and D, Example C includes a 7.1:1 ratio by weightbetween egg albumen and spinetoram, a 1.6:1 ratio by weight betweenpolyvinyl alcohol and spinetoram and a 4.4:1 ratio by weight between eggalbumen and polyvinyl alcohol, while Example D includes a 7.1:1 ratio byweight between egg albumen and spinetoram, a 1.6:1 ratio by weightbetween polyvinyl alcohol and spinetoram and a 4.4:1 ratio by weightbetween egg albumen and polyvinyl alcohol. With respect to Examples Eand F, G, and H, Example E includes a 1.7:1 ratio by weight between iron(III) oxide and spinetoram, a 0.2:1 ratio by weight between Agrimer VA 6and spinetoram and a 0.1:1 ratio by weight Agrimer VA 6 and iron (III)oxide, while Examples F. G and H each include a 1.7:1 ratio by weightbetween iron (III) oxide and spinetoram, a 0.2:1 ratio by weight betweenAgrimer VA 6 and spinetoram and a 0.1:1 ratio by weight between AgrimerVA 6 and iron (III) oxide. Each of the weight ratios set forth above inthis paragraph was rounded to the nearest tenth.

Bio-Efficacy Testing

Biological efficacy experiments were conducted according to thefollowing parameters. A spinetoram control solution was preparedutilizing either Radiant®, a suspension concentrate formulation ofspinetoram, or Delegate®, a water-dispersible granule formulation ofspinetoram, in water to obtain a spinetoram concentration in solution of125 ppm. Radiant® and Delegate® are commercially available from DowAgroSciences LLC, 9330 Zionsville Road, Indianapolis, Ind., 46268. Testsolutions were also prepared utilizing the liquid compositions ofExamples A, C and E and the solid compositions of Examples B, D and F-H(collectively the Example A-H solutions) in water to obtain a spinetoramconcentration in each solution of 125 ppm, These solutions, plus awater-only control, were applied to potted pepper plants (Capsicumannuum) using a Mandel track sprayer calibrated to deliver theequivalent of 200 L/Ha of spray. Treated plants were allowed to dry andthen were aged outdoors in natural sunlight or under a set of lampsemitting ultraviolet light at levels comparable to natural sunlight. Atthe appropriate time after treatment, i.e., at 4, 7 and 10; 4, 7 and 11;or 5 and 10 days after treatment, 2.5 cm diameter disks were cut fromtreated leaves. One leaf disk was placed in each well of a 32 wellplastic tray, which also contained a thin layer of agar to providemoisture. There were 8 replicate disks per treatment. Each well wasinfested with three second instar beet armyworm (Spodoptera exigua)larvae, and the well was sealed with plastic film. Larvae were held inan environmental chamber at 25° C./40 percent relative humidity. At 48hours after infestation, the larvae were graded for mortality. A larvawas considered dead if it could not move after being prodded, and thepercent mortality (percent control) was calculated.

For Examples I-IV, Table 9 below provides the percent control of theinsect associated with the spinetoram control solution relative to anuntreated standard. For the Example A-H solutions, Table 9 provides theimprovement in percent control relative to the spinetoram controlsolution (i.e., (percent control by Example A-H solutions)—(percentcontrol by spinetoram control solution)). Table 9 also provides theaverage improvement over the spinetoram control solution which wascalculated by summing the individual improvements for each of the daysrelative to the control and then dividing by the number of measurements.As illustrated in Table 9, the Example B, D and F-H solutions, whichutilized the solid compositions provided by the spray drying, exhibitedenhanced pesticidal activity relative to the Example A, C and Esolutions, respectively.

TABLE 9 Example 3 4 5 6 7 9 10 11 12 13 14 Average Composition DAT DATDAT DAT DAT DAT DAT DAT DAT DAT DAT Improvement Example I Spinetoram —88 — — 25 —  8 — — — — Control Solution Example A —  8 — — 33 — 17 — — —— 19 Solution Example B —  4 — — 58 — 58 — — — — 40 Solution Example IISpinetoram — 67 — — 33 — — 25 — — — Control Solution Example C — 21 — —29 — — −21  — — — 10 Solution Example D — 33 — — 58 — — 29 — — — 40Solution Example III Spinetoram 58 17 Control Solution Example E 21 2121 Solution Example G 25 41 33 Solution Example H 25 50 38 SolutionExample IV Spinetoram 75  8 Control Solution Example F 25 88 57 Solution

The headings in this document are for convenience only and must not beused to interpret any portion thereof.

Any theory, mechanism of operation, proof, or finding stated herein ismeant to further enhance understanding of the present invention and isnot intended to make the present invention in any way dependent uponsuch theory, mechanism of operation, proof, or finding. It should beunderstood that while the use of the word preferable, preferably orpreferred in the description above indicates that the feature sodescribed may be more desirable, it nonetheless may not be necessary andembodiments lacking the same may be contemplated as within the scope ofthe invention, that scope being defined by the claims that follow. Inreading the claims it is intended that when words such as “a,” “an,” “atleast one,” “at least a portion” are used there is no intention to limitthe claim to only one item unless specifically stated to the contrary inthe claim. Further, when the language “at least a portion” and/or “aportion” is used the item may include a portion and/or the entire itemunless specifically stated to the contrary. While the invention has beenillustrated and described in detail in the drawings and foregoingdescription, the same is to be considered as illustrative and notrestrictive in character, it being understood that only the selectedembodiments have been shown and described and that all changes,modifications and equivalents that come within the spirit of theinvention as defined herein or by any of the following claims aredesired to be protected.

What is claimed is:
 1. A method, comprising: providing a liquidcomposition that includes: at least one of spinetoram and spinosad; andone of (a)-(c): (a) an iron oxide or zinc oxide and a proteinaceousmaterial selected from the group consisting of an amino acid, bovineserum albumin, egg albumen, whey, gelatin and zein; (b) an iron oxide orzinc oxide and a polymeric material that includes at least one ofpolyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetate, vinylpyrrolidone and vinyl acetate; and (c) a proteinaceous material and apolymeric material, wherein the proteinaceous material is selected fromthe group consisting of an amino acid, bovine serum albumin, eggalbumen, whey, gelatin and zein and the polymeric material includes atleast one of polyvinyl alcohol, polyvinyl pyrrolidone, polyvinylacetate, vinyl pyrrolidone and vinyl acetate; and spray drying theliquid composition to provide a solid composition.
 2. The method ofclaim 1, wherein the spray drying is performed at a feed rate in therange of 200 to 500 mL/hr.
 3. The method of claim 1, wherein the liquidcomposition includes (b) and the polymeric material is a vinylpyrrolidone/vinyl acetate copolymer.
 4. The method of claim 3, whereinthe liquid composition includes ferric oxide.
 5. The method of claim 1,wherein the liquid composition includes an average particle size in therange of 1-10 μm.
 6. The method of claim 1, wherein the liquidcomposition includes (a) and the proteinaceous material is egg albumen.7. The method of claim 6, wherein the liquid composition includes zincoxide.
 8. The method of claim 1, wherein the liquid composition includes(c) and the proteinaceous material is egg albumen and the polymericmaterial is polyvinyl alcohol.
 9. The method of claim 1, wherein theliquid composition includes (a) and the proteinaceous material and theiron oxide or zinc oxide are present at a ratio by weight of about1.5:1.
 10. The method of claim 1, wherein the liquid compositionincludes (b) and the iron oxide or zinc oxide and the polymeric materialare present at a ratio by weight of about 11:1.
 11. The method of claim1, wherein the liquid composition includes (c) and the proteinaceousmaterial and the polymeric material are present at a ratio by weight ofabout 4.5:1.
 12. The method of claim 1, wherein the liquid compositionincludes water and the spray drying includes at least partiallydehydrating the liquid composition.